Piezoelectric element, liquid ejecting head, and liquid ejecting apparatus

ABSTRACT

A piezoelectric element comprises a piezoelectric layer comprising a mixed crystal including at least cerium, bismuth, iron, barium, and titanium and an electrode provided to the piezoelectric layer. The molar ratio of cerium to the total amount of cerium and bismuth in the piezoelectric layer is 0.03 or more and 0.10 or lower.

CROSS-REFERENCE TO RELATED APPLICATIONS

The entire disclosure of Japanese Patent Application No. 2011-027919, filed Feb. 10, 2011 is expressly incorporated by reference.

BACKGROUND

1. Technical Field

The present invention relates to a liquid ejecting head provided with a piezoelectric element which causes a change in the pressure of pressure generating chambers communicating with nozzle openings and which has a piezoelectric layer and electrodes which apply a voltage to the piezoelectric layer, a liquid ejecting apparatus, and a piezoelectric element.

2. Related Art

Mentioned as the piezoelectric element is one in which a piezoelectric layer (piezoelectric film) containing a piezoelectric material which exhibits an electromechanical conversion function, e.g., a crystallized piezoelectric material, is sandwiched between two electrodes. Such a piezoelectric element is mounted as an actuator device of a bending vibration mode, for example, on a liquid ejecting head. Mentioned as a typical example of the liquid ejecting head is, for example, an ink jet recording head in which a part of pressure generating chambers communicating with nozzle openings which eject ink droplets is constituted by a diaphragm, and the diaphragm is transformed by a piezoelectric element to pressurize ink in the pressure generating chambers, whereby the ink is ejected from the nozzle openings in the form of ink droplets.

The piezoelectric material used as the piezoelectric layer constituting such a piezoelectric element has been required to have high piezoelectric properties, and lead zirconate titanate (PZT) is mentioned as a typical example thereof (Japanese Unexamined Patent Application Publication No. 2001-223404). However, a piezoelectric material in which the lead content is reduced has been demanded from the viewpoint of environmental problems. Mentioned as piezoelectric materials not containing lead are BiFeO₃ piezoelectric materials containing Bi and Fe, for example. Mentioned as a specific example thereof are complex oxides represented as a mixed crystal of bismuth ferrate manganate, such as Bi(Fe,Mn)O₃ and barium titanate, such as BaTiO₃, (e.g., Japanese Unexamined Patent Application Publication No. 2009-252789).

Such a piezoelectric material containing the mixed crystal of bismuth ferrate manganate and barium titanate has a relatively small distortion. The distortion can be increased by applying a high voltage. However, when a high voltage is applied, there arises a problem that dielectric breakdown arises in some cases. Therefore, it has been required to prevent dielectric breakdown even when a high voltage is applied, i.e., to increase the withstand voltage. Moreover, in order to suppress the occurrence of cracking, the equalization of the crystal grain size has also been required. Such a problem is not limited to the liquid ejecting head typified by the ink jet recording head, and similarly arises in other piezoelectric elements.

SUMMARY

An advantage of some aspects of the invention is to provide a liquid ejecting head provided with a piezoelectric element having a piezoelectric layer with a high withstand voltage and a uniform crystal grain size, a liquid ejecting apparatus, and a piezoelectric element.

An embodiment of the invention which solves the above-described problems provides a liquid ejecting head having a pressure generating chamber communicating with a nozzle opening and a piezoelectric element having a piezoelectric layer and an electrode provided on the piezoelectric layer, in which the piezoelectric layer is a complex oxide represented as a mixed crystal of cerium bismuth ferrate manganate and barium titanate and has Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi of 0.03 or more and 0.10 or lower.

According to the embodiment, by employing the piezoelectric layer which is a complex oxide represented as the mixed crystal of cerium bismuth ferrate manganate and barium titanate and has Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi of 0.03 or more and 0.10 or lower, the withstand voltage can be made high. Therefore, dielectric breakdown is prevented even when a high voltage is applied. Moreover, since the crystal grain size of the piezoelectric layer is uniformized, the occurrence of cracking in the piezoelectric layer can be suppressed. The piezoelectric layer has good hysteresis characteristics, and the piezoelectric properties are also excellent.

Another embodiment of the invention provides a liquid ejecting apparatus having the above-described liquid ejecting head. According to the embodiment, since the piezoelectric element is provided in which dielectric breakdown is prevented even when a high voltage is applied, and the occurrence of cracking is suppressed, a liquid ejecting apparatus excellent in durability and reliability can be achieved.

Another embodiment of the invention provides a piezoelectric element having a piezoelectric layer and an electrode provided on the piezoelectric layer, in which the piezoelectric layer is a complex oxide represented as a mixed crystal of cerium bismuth ferrate manganate and barium titanate and has Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi of 0.03 or more and 0.10 or lower. According to the embodiment, by employing the piezoelectric layer which is a complex oxide represented as the mixed crystal of cerium bismuth ferrate manganate and barium titanate and has Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi of 0.03 or more and 0.10 or lower, the withstand voltage can be increased. Therefore, dielectric breakdown is prevented even when a high voltage is applied. Moreover, since the crystal grain size of the piezoelectric layer is uniformized, the occurrence of cracking in the piezoelectric layer can be suppressed. The piezoelectric layer has good hysteresis characteristics and the piezoelectric properties are also excellent.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described with reference to the accompanying drawings, wherein like numbers reference like elements.

FIG. 1 is an exploded perspective view schematically illustrating the structure of a recording head according to a first embodiment.

FIG. 2 is a plan view of the recording head according to the first embodiment.

FIG. 3 is a cross sectional view of the recording head according to the first embodiment.

FIGS. 4A and 4B are cross sectional views illustrating manufacturing processes of the recording head according to the first embodiment.

FIGS. 5A to 5C are cross sectional views illustrating manufacturing processes of the recording head according to the first embodiment.

FIGS. 6A and 6B are cross sectional views illustrating manufacturing processes of the recording head according to the first embodiment.

FIGS. 7A to 7C are cross sectional views illustrating manufacturing processes of the recording head according to the first embodiment.

FIGS. 8A and 8B are cross sectional views illustrating manufacturing processes of the recording head according to the first embodiment.

FIG. 9 is a view illustrating the X ray diffraction patterns of Examples 1 to 4 and Comparative Examples 1 to 3.

FIGS. 10A to 10D are views illustrating the P-V curves of Examples 1 to 3 and Comparative Example 1.

FIGS. 11A to 11C are views illustrating the P-V curves of Example 4 and Comparative Examples 2 and 3.

FIGS. 12A to 12G are photographs in which the surface of the piezoelectric layers of Examples 1 to 4 and Comparative Examples 1 to 3 is observed.

FIG. 13 is a view schematically illustrating the structure of a recording device according to one embodiment of the invention.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Embodiment 1

FIG. 1 is an exploded perspective view schematically illustrating the structure of an ink jet recording head which is one example of a liquid ejecting head according to a first embodiment of the invention. FIG. 2 is a plan view of FIG. 1. FIG. 3 is a cross sectional view along the III-III line of FIG. 2. As illustrated in FIGS. 1 to 3, a flow path formation substrate 10 of this embodiment contains a silicon single crystal substrate, and an elastic film 50 containing silicon dioxide is formed on one surface thereof.

In the flow path formation substrate 10, a plurality of pressure generating chambers 12 are arranged in parallel in the width direction. Moreover, a communication portion 13 is formed in a region at the outside in the longitudinal direction of the pressure generating chambers 12 of the flow path formation substrate 10, and the communication portion 13 and each pressure generating chamber 12 are made to communicate with each other through an ink supply path 14 and a communication path 15 provided every pressure generating chamber 12. The communication portion 13 communicates with a manifold portion 31 of a protective substrate described later to constitute a part of a manifold serving as a common ink chamber of the respective pressure generating chambers 12. The ink supply paths 14 are formed with a width narrower than that of the pressure generating chambers 12 and maintain the flow path resistance of ink flowing into the pressure generating chambers 12 from the communication portion 13 at a fixed level. In this embodiment, the ink supply paths 14 are formed by reducing the width of the flow path from one side but the ink supply paths may be formed by reducing the width of the flow path from both sides. Or, the ink supply paths may be formed by not reducing the width of the flow path but reducing the thickness thereof. In this embodiment, the flow path formation substrate 10 is provided with a liquid flow path containing the pressure generating chambers 12, the communication portion 13, the ink supply paths 14, and the communication paths 15.

To an opening surface side of the flow path formation substrate 10, a nozzle plate 20 in which nozzle openings 21 are formed which communicate with the vicinity of the end portion at the side opposite to the ink supply path 14 of each pressure generating chamber 12 is adhered with an adhesive, a thermal fusing film, or the like. The nozzle plate 20 contains, for example, glass ceramics, a silicon single crystal substrate, stainless steel, or the like.

In contrast, the elastic film 50 is formed on the surface opposite to the opening surface of such a flow path formation substrate 10 as described above. On the elastic film 50, an adhesion layer 56 is provided which contains titanium oxide having a thickness of about 30 to 50 nm or the like, for example, and which increases the adhesiveness with the foundation of a first electrode 60 of the elastic film 50 or the like. On the elastic film 50, an insulator film containing zirconium dioxide or the like may be provided as required.

Furthermore, on this adhesion layer 56, the first electrode 60, an piezoelectric layer 70 which is a thin film having a thickness of 3 μm or lower and preferably 0.3 to 1.5 μm, and a second electrode 80 are laminated to constitute a piezoelectric element 300. Herein, the piezoelectric element 300 refers to a portion containing the first electrode 60, the piezoelectric layer 70, and the second electrode 80. In general, the piezoelectric element 300 is configured so that either one of the electrodes of the piezoelectric element 300 is used as a common electrode and the other electrode and the piezoelectric layer 70 are patterned every pressure generating chamber 12. In this embodiment, the first electrode 60 is used as the common electrode of the piezoelectric element 300 and the second electrode 80 is used as an individual electrode of the piezoelectric element 300. However, even when the configuration is reversed due to a drive circuit or wiring, no problems arise. Herein, the piezoelectric element 300 and a diaphragm which causes displacement by the drive of the piezoelectric element 300 are collectively referred to as an actuator device. In the above-described example, the elastic film 50, the adhesion layer 56, the first electrode 60, and the insulator film provided as required acts as a diaphragm. However, it is a matter of course that the invention is not limited thereto and the elastic film 50 or the adhesion layer 56 may not be provided, for example. It may be configured so that the piezoelectric element 300 itself substantially serves also as a diaphragm.

In this embodiment, the piezoelectric material constituting the piezoelectric layer 70 is a complex oxide having a perovskite structure represented as a mixed crystal of cerium bismuth ferrate manganate and barium titanate and has Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi of 0.03 or more and 0.10 or lower.

In detail, as described in Japanese Unexamined Patent Application Publication No. 2009-252789 and the like, known as the piezoelectric material is a complex oxide represented as the mixed crystal of bismuth ferrate manganate and barium titanate, i.e., a complex oxide represented as a solid solution in which bismuth ferrate manganate and barium titanate forms a uniform solid solution. In this embodiment, a piezoelectric material obtained by adding raw materials containing Ce which is a tetravalent element, such as cerium 2-ethylhexanoate or triethoxy cerium, when manufacturing the complex oxide represented as the mixed crystal of bismuth ferrate manganate and barium titanate, and then replacing Bi of the complex oxide represented as the mixed crystal of bismuth ferrate manganate and barium titanate by Ce is formed into the piezoelectric layer 70. In the X ray diffraction pattern, the bismuth ferrate manganate, the barium titanate, or the cerium bismuth ferrate manganate is not solely detected.

Furthermore, in the invention, Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is 0.03 or more and 0.10 or lower in the piezoelectric layer 70.

Thus, when a complex oxide which is represented as a mixed crystal of cerium bismuth ferrate manganate and barium titanate and has Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi of 0.03 or more and 0.10 or lower is used as the piezoelectric material constituting the piezoelectric layer 70, the withstand voltage can be made high as compared with a system not containing Ce, i.e., the complex oxide represented as the mixed crystal of bismuth ferrate manganate and barium titanate, as shown in Test Examples described later. Therefore, an ink jet recording head is obtained in which even when a high voltage is applied, dielectric breakdown does not occur and the durability is excellent. Since a high voltage can be applied, the distortion can be increased. Therefore, an ink jet recording head having excellent ejection properties is obtained. Moreover, since the crystal grain size of the piezoelectric layer 70 is uniformized, the occurrence of cracking in the piezoelectric layer 70 can be suppressed. Therefore, an ink jet recording head having excellent reliability is obtained.

Here, by compounding Ce in the complex oxide represented as the mixed crystal of bismuth ferrate manganate and barium titanate, the withstand voltage can be made high and the crystal grain size can be uniformized. However, when the Ce content is extremely high, a piezoelectric layer which does not present a good hysteresis shape is obtained. When such as piezoelectric layer which does not present a good hysteresis shape is provided, the piezoelectric properties (distortion) deteriorate.

When Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is in the range of 0.03 or more and 0.10 or lower, the piezoelectric layer 70 does not have a hetero phase, such as a pyrochlore phase, as shown in Examples described later. The pyrochlore phase is observed at 2θ=25 to 30°, when the piezoelectric layer 70 is measured by an X ray diffraction wide angle method (XRD). The fact that “does not have a pyrochlore phase” refers to the fact that a peak is not observed at 2θ=25 to 30° in the XRD measurement.

Such a piezoelectric layer 70 has a perovskite structure as described above, i.e., ABO₃ structure, in which 12 oxygen atoms are coordinated in the A site of the structure and, in the B site thereof, 6 oxygen atoms are coordinated to form a octahedron. Bi and Ba are located in the A site, Fe, Mn, and Ti are located in the B site, and Ce replaces a part of Bi of the A site. More specifically, it is presumed that the complex oxide having a perovskite structure represented as the mixed crystal of cerium bismuth ferrate manganate and barium titanate has a structure in which a part of Bi of a solid solution in which bismuth ferrate manganate and barium titanate forms a uniform solid solution is replaced by Ce.

The piezoelectric layer 70 containing the complex oxide having such a perovskite structure is a mixed crystal represented by Formula (1), for example. (1−x)[(Bi_(1−a),Ce_(a))(Fe_(1−b),Mn_(b))O₃]−x[BaTiO₃]  (1) (0<x<0.40,0.03≦a≦0.10,0.01<b<0.10)

To each second electrode 80 which is an individual electrode of such a piezoelectric element 300, a lead electrode 90 is connected which contains, for example, gold (Au) or the like and which is drawn out from the vicinity of the end portion at the side of the ink supply paths 14 to be extended onto the elastic film 50 or the insulator film provided as required.

Onto the flow path formation substrate 10 on which such a piezoelectric element 300 is formed, i.e., onto the first electrode 60, the elastic film 50, the insulator film provided as required, and the lead electrode 90, a protective substrate 30 having the manifold portion 31 constituting at least one part of a manifold 100 is bonded through an adhesive 35. In this embodiment, the manifold portion 31 is formed penetrating the protective substrate 30 in the thickness direction over the width direction of the pressure generating chambers 12 and is made to communicate with the communication portion 13 of the flow path formation substrate 10 to constitute the manifold 100 which serves as a common ink chamber of the respective pressure generating chamber 12 as described above. The communication portion 13 of the flow path formation substrate 10 may be divided into a plurality of parts every pressure generating chamber 12, so that only the manifold portion 31 may be used as a manifold. Furthermore, for example, only the pressure generating chambers 12 may be provided in the flow path formation substrate 10, and the ink supply paths 14 communicating the manifold 100 and each pressure generating chamber 12 may be provided in a member (e.g., the elastic film 50, the insulator film provided as required, etc.) interposed between the flow path formation substrate 10 and the protective substrate 30.

In a region facing the piezoelectric element 300 of the protective substrate 30, a piezoelectric element holding portion 32 having a space large enough not to inhibit the movement of the piezoelectric element 300 is provided. The piezoelectric element holding portion 32 may have a space large enough not to inhibit the movement of the piezoelectric element 300, and the space may be or may not be sealed.

As such a protective substrate 30, a material having substantially the same coefficient of thermal expansion as that of the flow path formation substrate 10, e.g., glass and ceramic materials, is preferably used. In this embodiment, a silicon single crystal substrate which is the same material as the flow path formation substrate 10 is used for the formation thereof.

The protective substrate 30 is provided with a through hole 33 penetrating the protective substrate 30 in the thickness direction. The vicinity of the end portion of the lead electrode 90 drawn out from each piezoelectric element 300 is provided in such a manner as to be exposed to the inside of the through hole 33.

On the protective substrate 30, a drive circuit 120 for driving the piezoelectric elements 300 arranged in parallel is fixed. As the drive circuit 120, a circuit substrate, a semiconductor integrated circuit (IC), or the like can be used, for example. The drive circuit 120 and the lead electrode 90 are electrically connected through a connection wiring 121 containing a conductive wire, such as a bonding wire.

Onto such a protective substrate 30, a compliance substrate 40 containing a sealing film 41 and a fixation plate 42 is bonded. Herein, the sealing film 41 contains a material having a low rigidity and flexibility, and the sealing film 41 seals one surface of the manifold portion 31. The fixation plate 42 is formed with a relatively hard material. A region facing the manifold 100 of the fixation plate 42 is completely removed in the thickness direction to form an opening portion 43, and therefore one surface of the manifold 100 is sealed only by the sealing film 41 having flexibility.

In such an ink jet recording head I of this embodiment, ink is taken in from an ink introduction port connected to an ink supply unit (not illustrated) at the outside, the inside of a space from the manifold 100 to the nozzle opening 21 is filled with the ink, and thereafter a voltage is applied to the first electrode 60 and the second electrode 80 corresponding to each of the pressure generating chambers 12 in accordance with a recording signal from the drive circuit 120 to bend and transform the elastic film 50, the adhesion layer 56, the first electrode 60, and the piezoelectric layer 70, so that the pressure in each pressure generating chamber 12 increases, and ink droplets are ejected from the nozzle openings 21. In the invention, since the withstand voltage is high, dielectric breakdown of the piezoelectric element 300 does not occur even when a high voltage is applied. Therefore, a high voltage can be applied for driving.

Next, an example of a method for manufacturing the ink jet recording head of this embodiment is described with reference to FIGS. 4 to 8. FIGS. 4 to 8 are cross sectional views in the longitudinal direction of the pressure generating chamber.

First, as illustrated in FIG. 4A, a silicon dioxide film containing silicon dioxide (SiO₂) or the like constituting the elastic film 50 is formed by thermal oxidation or the like on the surface of a flow path formation substrate wafer 110 which is a silicon wafer. Subsequently, as illustrated in FIG. 4B, the adhesion layer 56 containing titanium oxide or the like is formed on the elastic film 50 (silicon dioxide film) by sputtering, thermal oxidation, or the like.

Next, as illustrated in FIG. 5A, the first electrode 60 containing platinum, iridium, iridium oxide, or a laminated structure thereof is formed on the entire surface of the adhesion layer 56 by sputtering, vapor deposition, or the like.

Subsequently, the piezoelectric layer 70 is laminated on the platinum film. A method for manufacturing the piezoelectric layer 70 is not particularly limited. For example, the piezoelectric layer 70 can be manufactured using a chemical solution method, such as an MOD (Metal-Organic Decomposition) method or a sol-gel method including applying a solution containing a metal complex and drying the same, and then further baking the same at a high temperature to thereby obtain a piezoelectric layer (piezoelectric film) containing metal oxide. In addition thereto, the piezoelectric layer 70 can also be manufactured by not only a liquid phase method but a solid phase method, such as a laser ablation method, a sputtering method, a pulsed laser deposition method (PLD method), a CVD method, an aerosol deposition method, or the like.

As a specific example of a formation procedure for forming the piezoelectric layer 70 by the chemical solution method, first, a piezoelectric film formation composition (precursor solution) containing an MOD solution or a sol containing a metal complex, specifically, metal complexes containing Bi, Fe, Mn, Ba, Ti, and Ce, is applied onto the first electrode 60 using a spin coat method or the like to thereby form a piezoelectric precursor film 71 as illustrated in FIG. 5B (application process).

The precursor solution to apply is one obtained by mixing metal complexes which contain Bi, Fe, Mn, Ba, Ti, and Ce and are capable of forming complex oxides, and dissolving or dispersing the mixture in organic solvents. The mixing ratio of the metal complexes each containing Bi, Fe, Mn, Ba, and Ti is determined in such a manner as to form a desired complex oxide having a perovskite structure represented as the mixed crystal of bismuth ferrate manganate and barium titanate. The mixing ratio of the metal complex containing Ce is determined in such a manner that Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is 0.03 or more and 0.10 or lower. As the metal complexes each containing Bi, Fe, Mn, Ba, Ti, and Ce, alkoxide, organic acid salt, βdiketone complex, and the like can be used, for example. As the metal complex containing Bi, bismuth 2-ethylhexanoate, bismuth acetate, and the like are mentioned, for example. As the metal complex containing Fe, iron 2-ethylhexanoate, iron acetate, and the like are mentioned, for example. As the metal complex containing Mn, manganese 2-ethylhexanoate, manganese acetate, and the like are mentioned, for example. As the metal complex containing Ba, barium isopropoxide, barium 2-ethyl hexanoate, barium acetylacetonato, and the like are mentioned, for example. As the metal complex containing Ti, titanium isopropoxide, titanium 2-ethylhexanoate, titanium(di-i-propoxide)bis(acetylacetonato), and the like are mentioned, for example. As the metal complex containing Ce, cerium 2-ethylhexanoate, triethoxy cerium, and the like are mentioned, for example. It is a matter of course that metal complexes containing two or more kinds of Bi, Fe, Mn, Ba, Ti, and Ce may be used.

Subsequently, the piezoelectric precursor film 71 is heated to a predetermined temperature (e.g., 150 to 200° C.), and is dried for a given period of time (drying process). Next, the dried piezoelectric precursor film 71 is heated to a predetermined temperature (e.g., 350 to 450° C.), and then held for a given period of time for degreasing (degreasing process). The degreasing as used herein is to remove the organic components contained in the piezoelectric precursor film 71 as NO₂, CO₂, H₂O, and the like, for example. The atmosphere of the drying process or the degreasing process is not limited, and the processes may be performed in the air, an oxygen atmosphere, or inactive gas. The application process, the drying process, and the degreasing process may be performed two or more times.

Next, as illustrated in FIG. 5C, the piezoelectric precursor film 71 is heated to a predetermined temperature, e.g., about 600 to 850° C., and then held for a given period of time, e.g., 1 to 10 minutes, for crystallizing to thereby form a piezoelectric film 72 containing a piezoelectric material which is a complex oxide having a perovskite structure represented as the mixed crystal of cerium bismuth ferrate manganate and barium titanate and has Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi of 0.03 or more and 0.10 or lower (baking process). Also in this baking process, the atmosphere is not limited, and the baking process may be performed in the air, an oxygen atmosphere, or inactive gas.

As a heating device for use in the drying process, the degreasing process, and the baking process, an RTA (Rapid Thermal Annealing) device which heats by irradiation of an infrared lamp, a hot plate, and the like are mentioned, for example.

Next, as illustrated in FIG. 6A, the first electrode 60 and a first layer of the piezoelectric film 72 are simultaneously patterned on the piezoelectric film 72 using a resist (not illustrated) having a predetermined shape as a mask in such a manner that the side surfaces thereof incline.

Subsequently, the resist is separated, and thereafter the application process, the drying process, and the degreasing process described above or the application process, the drying process, the degreasing process, and the baking process described above are repeated two or more times in accordance with a desired film thickness to thereby form the piezoelectric layer 70 containing a plurality of the piezoelectric films 72, whereby the piezoelectric layer 70 having a predetermined thickness containing a plurality of the piezoelectric films 72 is formed as illustrated in FIG. 6B. For example, when the film thickness per application of the application solution is about 0.1 μm, the film thickness of the entire piezoelectric layer 70 containing 10 layers of the piezoelectric films 72 is about 1.1 μm. In this embodiment, the piezoelectric films 72 are laminated, but only one piezoelectric film 72 may be acceptable.

After forming the piezoelectric layer 70 as described above, the second electrode 80 containing platinum or the like is formed on the piezoelectric layer 70 by sputtering or the like, and then the piezoelectric layer 70 and the second electrode 80 are simultaneously patterned in a region facing each pressure generating chamber 12, thereby forming the piezoelectric element 300 containing the first electrode 60, the piezoelectric layer 70, and the second electrode 80 as illustrated in FIG. 7A. The patterning of the piezoelectric layer 70 and the patterning of the second electrode 80 can be collectively carried out by performing dry etching through a resist (not illustrated) formed into a predetermined shape. Thereafter, for example, annealing may be performed in a temperature range of 600 to 850° C. as required. Thus, a good interface of the piezoelectric layer 70 and the first electrode 60 or the second electrode 80 can be formed and the crystallinity of the piezoelectric layer 70 can be improved.

Next, as illustrated in FIG. 7B, the lead electrode 90 containing, for example, gold (Au) or the like is formed on the entire surface of the flow path formation substrate wafer 110, and thereafter patterned every piezoelectric element 300 through a mask pattern (not illustrated) containing resist or the like, for example.

Next, as illustrated in FIG. 7C, a protective substrate wafer 130 which is a silicon wafer and serves as a plurality of protective substrates 30 is bonded to the piezoelectric element 300 side of the flow path formation substrate wafer 110 through the adhesive 35, and thereafter the thickness of the flow path formation substrate wafer 110 is reduced to a predetermined thickness.

Next, as illustrated in FIG. 8A, a mask film 52 is newly formed on the flow path formation substrate wafer 110, and then patterned into a predetermined shape.

Then, as illustrated in FIG. 8B, by anisotropically etching (wet etching) the flow path formation substrate wafer 110 using an alkaline solution of KOH or the like through the mask film 52, the pressure generating chamber 12, the communication portion 13, the ink supply path 14, the communication path 15, and the like corresponding to the piezoelectric element 300 are formed.

Thereafter, unnecessary portions of the outer peripheral edge portion of the flow path formation substrate wafer 110 and the protective substrate wafer 130 are removed by cutting by dicing or the like, for example. Then, the mask film 52 on the surface opposite to the protective substrate wafer 130 of the flow path formation substrate wafer 110 is removed, the nozzle plate 20 in which the nozzle openings 21 are formed is bonded, the compliance substrate 40 is bonded to the protective substrate wafer 130, and then the flow path formation substrate wafer 110 and the like are divided into the flow path formation substrate 10 of one chip size and the like as illustrated in FIG. 1, thereby manufacturing the ink jet recording head I of this embodiment.

EXAMPLES

Hereinafter, Examples are shown, and the invention is more specifically described. The invention is not limited to the following Examples.

Example 1

First, a silicon oxide (SiO₂) film was formed on the surface of a single crystal silicon (Si) substrate by thermal oxidation. Next, on the SiO₂ film, a zirconium film was produced by sputtering, followed by thermal oxidation, thereby forming a zirconium oxide film. Next, a titanium oxide having a thickness of 40 nm was laminated on the zirconium oxide film, and then a platinum film (first electrode 60) which is oriented in the (111) plane and which has a thickness of 100 nm was formed thereon.

Subsequently, the piezoelectric layer 70 was formed on the first electrode 60 by spin coating. The technique is as follows. First, n-octane solvent solutions of bismuth 2-ethylhexanoate, iron 2-ethylhexanoate, manganese 2-ethylhexanoate, barium 2-ethylhexanoate, titanium 2-ethylhexanoate, and cerium 2-ethylhexanoate were mixed with a predetermined ratio to thereby prepare a precursor solution.

Then, the precursor solution was added dropwise on the substrate on which the titanium oxide film and the platinum film were formed, and the substrate was rotated at 2500 rpm, thereby forming a piezoelectric precursor film (application process). Next, drying was performed at 180° C. for 3 minutes (drying process). Subsequently, degreasing was performed at 450° C. for 3 minutes (degreasing process). After a process including the application process, the drying process, and the degreasing process was repeatedly performed twice, baking was performed at 800° C. for 5 minutes in an oxygen atmosphere by an RTA (Rapid Thermal Annealing) device (baking process). Subsequently, a process including repeating the application process, the drying process, and the degreasing process twice, and thereafter performing the baking process for collectively baking was repeated 5 times, thereby forming the piezoelectric layer 70 having the total thickness of 700 nm by the ten application processes in total.

Thereafter, a platinum film (second electrode) having a thickness of 100 nm was formed as the second electrode 80 on the piezoelectric layer 70 by sputtering, followed by baking at 800° C. for 5 minutes in an oxygen atmosphere using an RTA device, thereby forming the piezoelectric element 300 in which a piezoelectric material is a complex oxide which has a perovskite structure represented as a mixed crystal of cerium bismuth ferrate manganate and barium titanate and has Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi of 0.03, specifically a complex oxide containing a mixed crystal represented by 0.75[(Bi_(0.97), Ce_(0.03)) (Fe_(0.95), Mn_(0.05))O₃]-0.25[BaTiO₃] was formed into the piezoelectric layer 70.

Example 2

The same operation as in Example 1 was performed, except changing the addition amount of bismuth 2-ethylhexanoate and cerium 2-ethylhexanoate to the precursor solution and forming a piezoelectric material in which Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is 0.05, specifically a complex oxide containing a mixed crystal represented by 0.75[(Bi_(0.95), Ce_(0.05)) (Fe_(0.95), Mn_(0.05))O₃]-0.25[BaTiO₃] into the piezoelectric layer 70.

Example 3

The same operation as in Example 1 was performed, except changing the addition amount of bismuth 2-ethylhexanoate and cerium 2-ethylhexanoate to the precursor solution and forming a piezoelectric material in which Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is 0.07, specifically a complex oxide containing a mixed crystal represented by 0.75[(Bi_(0.93), Ce_(0.07))(Fe_(0.95), Mn_(0.05))O₃]-0.25[BaTiO₃] into the piezoelectric layer 70.

Example 4

The same operation as in Example 1 was performed, except changing the addition amount of bismuth 2-ethylhexanoate and cerium 2-ethylhexanoate to the precursor solution and forming a piezoelectric material in which Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is 0.10, specifically a complex oxide containing a mixed crystal represented by 0.75[(Bi_(0.90), Ce_(0.10))(Fe_(0.95), Mn_(0.05))O₃]-0.25[BaTiO₃] into the piezoelectric layer 70.

Comparative Example 1

The same operation as in Example 1 was performed, except not adding cerium 2-ethylhexanoate to the precursor solution and forming a complex oxide containing a mixed crystal represented by 0.75[Bi(Fe_(0.95), Mn_(0.05))O₃]-0.25[BaTiO₃] into the piezoelectric layer 70.

Comparative Example 2

The same operation as in Example 1 was performed, except changing the addition amount of bismuth 2-ethylhexanoate and cerium 2-ethylhexanoate to the precursor solution and forming a piezoelectric material in which Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is 0.12, specifically a complex oxide containing a mixed crystal represented by 0.75[(Bi_(0.88), Ce_(0.12))(Fe_(0.95), Mn_(0.05))O₃]-0.25[BaTiO₃] into the piezoelectric layer 70.

Comparative Example 3

The same operation as in Example 1 was performed, except changing the addition amount of bismuth 2-ethylhexanoate and cerium 2-ethylhexanoate to the precursor solution and forming a piezoelectric material in which Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is 0.15, specifically a complex oxide containing a mixed crystal represented by 0.75[(Bi_(0.85), Ce_(0.15))(Fe_(0.95), Mn_(0.05))O₃]-0.25[BaTiO₃] into the piezoelectric layer 70.

Test Example 1

In each piezoelectric element of Examples 1 to 4 and Comparative Examples 1 to 3, the X-ray diffraction pattern of the piezoelectric layer 70 was determined at room temperature (25° C.) using “D8 Discover” manufactured by Bruker AXS using a CuKα line as the X-ray source. The results are shown in FIG. 9.

As a result, in all of the Examples 1 to 4 and Comparative Examples 1 to 3, bismuth ferrate manganate, barium titanate, or cerium bismuth ferrate manganate was not solely detected. Moreover, in all of the Examples 1 to 4 and Comparative Examples 1 to 3, the peak derived from the perovskite structure and the peak derived from the substrate were observed. In all of the Examples 1 to 4 and Comparative Examples 1 to 3, hetero phases, such as a pyrochlore phase, were not observed, and single phase of a perovskite structure was presented.

Test Example 2

Each piezoelectric element of Examples 1 to 4 and Comparative Examples 1 to 3 was observed for the relationship of P (Polarization amount)−V (Voltage) by applying a triangular wave of 1 kHz frequency using an electrode pattern of φ=500 μm by “FCE-1A” manufactured by TOYO Corp. The result of Comparative Example 1 is shown in FIG. 10A. The result of Example 1 is shown in FIG. 10B. The result of Example 2 is shown in FIG. 10C. The result of Example 3 is shown in FIG. 10D. The result of 4 is shown in FIG. 11A. The result of Comparative Example 2 is shown in FIG. 11B. The result of Comparative Example 3 is shown in FIG. 11C. The vertical axis of each of FIG. 10 and FIG. 11 represents the values obtained by dividing the measured polarization amount by the maximum polarization amount, and normalizing the obtained value.

As a result, as illustrated in FIG. 10 and FIGS. 11, in Comparative Example 1 and Examples 1 to 4, a hysteresis shape is presented and it can be said that the piezoelectric properties (distortion) are good. In contrast, in Comparative Examples 2 and 3 in which Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is high, there is no point of inflection around 20 V, an elliptical shape is presented and a hysteresis shape is not presented, and the piezoelectric properties were not good.

Test Example 3

Each piezoelectric element of Examples 1 to 4 and Comparative Examples 1 to 3 was measured for the J-E Curve at room temperature using “4140B” manufactured by Hewlett Packard Co., and the withstand voltage value which is the voltage at which the piezoelectric element destroyed was determined. The results are shown in Table 1.

As a result, as shown in Table 1, in Examples 1 to 4 and Comparative Examples 2 and 3 in which Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is 0.03 or more and 0.15 or lower, the withstand voltage was higher than that of Comparative Example 1 not containing Ce.

TABLE 1 Ce/(Ce + Bi) Withstand voltage (molar ratio) (V) Comp. Example 1 0 58 Example 1 0.03 60 Example 2 0.05 60 Example 3 0.07 64 Example 4 0.10 68 Comp. Example 2 0.12 70 Comp. Example 3 0.15 76

Test Example 4

In the piezoelectric layer 70 in a state where the second electrode 80 was not formed in Examples 1 to 4 and Comparative Examples 1 to 3, the surface immediately after formation was observed under a scanning electron microscope (SEM) (×50,000). The result of Comparative Example 1 is shown in FIG. 12A. The result of Example 1 is shown in FIG. 12B. The result of Example 2 is shown in FIG. 12C. The result of Example 3 is shown in FIG. 12D. The result of Example 4 is shown in FIG. 12E. The result of Comparative Example 2 is shown in FIG. 12F. The result of Comparative Example 3 is shown in FIG. 12G.

As a result, as illustrated in FIGS. 12, the crystal grain size in Examples 1 to 4 in which Ce/(Ce+Bi) which is a molar ratio of Ce and the total amount of Ce and Bi is 0.03 or more and 0.10 or lower was finer and more uniform than that of Comparative Example 1 not containing Ce and Comparative Examples 2 and 3 in which the Ce/(Ce+Bi) is larger than 0.10.

Other Embodiments

One embodiment of the invention is described above, but the basic configuration of the invention is not limited to one described above. For example, although the silicon single crystal substrate is mentioned as an example of the flow path formation substrate 10 in the embodiment described above, the invention is not limited thereto. For example, materials, such as an SOI substrate and glass, may be used.

Furthermore, in the embodiment described above, although the piezoelectric element 300 in which the first electrode 60, the piezoelectric layer 70, and the second electrode 80 are successively laminated on the substrate (flow path formation substrate 10) is mentioned as an example, the invention is not limited thereto. For example, the invention can be applied also to a longitudinal oscillation type piezoelectric element in which a piezoelectric material and an electrode formation material are alternately laminated and which is made to expand and contract in the axial direction.

The ink jet recording heads of these embodiments constitute a part of a recording head unit having an ink flow path communicating with an ink cartridge or the like and is mounted on an ink jet recording device. FIG. 13 is a view schematically illustrating one example of the ink jet recording device.

In an ink jet recording device II illustrated in FIG. 13, recording head units 1A and 1B having the ink jet recording head I are detachably provided with cartridges 2A and 2B constituting an ink supply unit, respectively, and a carriage 3 on which the recording head units 1A and 1B are mounted is provided to a carriage shaft 5 attached to a device body 4 in such a manner as to freely move in the axial direction. It is configured so that the recording head units 1A and 1B eject a black ink composition and a color ink composition, respectively, for example.

The carriage 3 on which the recording head units 1A and 1B are mounted is moved along the carriage shaft 5 by the transmission of the driving force of a drive motor 6 to the carriage 3 through a plurality of gears (not illustrated) and a timing belt 7. In the device body 4, a platen 8 is provided along the carriage shaft 5, and it is configured so that a recording sheet S which is a recording medium, such as paper, which is fed by a paper feed roller or the like (not illustrated) is wound around the platen 8 to be transported.

Although the embodiments described above describe the ink jet recording head as an example of a liquid ejecting head, the invention is widely targeted to general liquid ejecting heads. It is a matter of course that the invention can be applied to liquid ejecting heads which eject liquid other than ink. Mentioned as other liquid ejecting heads are, for example, various kinds of recording heads for use in image recording devices, such as printers, color material ejecting heads for use in the manufacturing of color filters of liquid crystal displays, electrode material ejecting heads for use in the formation of electrodes of organic EL displays, FED (Field Emission Display), and the like, biological organic material ejecting heads for use in the manufacturing of biochips, and the like.

The invention is not limited to the piezoelectric element mounted on liquid ejecting heads typified by ink jet recording heads and can also be applied to piezoelectric elements mounted on other devices, such as pyroelectric elements, such as ultrasonic devices, e.g., an ultrasonic transmitter, an ultrasonic motor, a pressure sensor, and IR sensor. The invention can be similarly applied also to ferroelectric elements, such as a ferroelectric memory. 

What is claimed is:
 1. A piezoelectric element, comprising: a piezoelectric layer comprising a mixed crystal including at least cerium, bismuth, iron, barium, and titanium; and an electrode provided to the piezoelectric layer, wherein the molar ratio of cerium to the total amount of cerium and bismuth (Ce/Ce+Bi) in the piezoelectric layer is 0.03 or more and 0.10 or lower.
 2. The piezoelectric element, according to claim 1, wherein the mixed crystal further includes manganese.
 3. A liquid ejecting head, comprising the piezoelectric element according to claim
 1. 4. A liquid ejecting apparatus, comprising the liquid ejecting head according to claim
 3. 